Recently, in the field of organic high molecular materials having an electron conductivity, the applications for batteries and various functional devices have been investigated.
Examples of such useful organic high molecular materials include polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, polyphenyleneacetylene, and polyacetylene and practical examples thereof are described in West German Patents 3,223,544, 3,318,856, 3,318,857, 3,325,892, 3,338,904, and 3,421,296, JP-A-58-187432, JP-A-59-43060, JP-A-59-112583, JP-A-58-209864, JP-A-59-207933, JP-A-60-120722, JP-A-60-67527, JP-A-62-225518, JP-A-62-53328, JP-A-63-199726, JP-A-60-223817, JP-A-61-83221, JP-A-59-31565, etc. (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
These high molecular materials are excellent in electron conductivity but have disadvantages that they are poor in mechanical strength, are reluctant to dissolve in solvent, and are poor in molding workability. Thus, electron conductive high molecular compounds having excellent electron conductivity and excellent molding workability have been desired.
As an electric conductive material, a combination of the layer of the electron conductive high molecular material and the layer of an electrolyte is used but for sufficiently functioning as electron devices or batteries, it is necessary to quickly conduct the exchange of electrons and ions at interface of both the elements.
It is reported that as an electrolyte, a high molecular solid electrolyte is excellent in the points of causing no liquid leakage, having a high mechanical strength, having a high flexibility of laminated layer material.
As the electrically conductive electronic material composed of combination of such a high molecular solid electrolyte and an electron conductive high molecular material, an organic battery composed of a combination of polyacetylene and a solid electrolyte is proposed in Polymer, Vol. 22, 1454-1455 (November, 1981), etc. However, the film of the polyacetylene prepared by an addition polymerization has problems that the oxidation stability is poor, the contact of the film with the high molecular solid electrode at the interface thereof is insufficient, whereby a good electric conductivity is not obtained, and also the response speed as a device material is slow.
Also, JP-A-62-98577 describes a laminated layer type electrically conductive material composed of a combination of a polymer having conjugated double bond at the main chain produced by an electrolytic polymerization and a high molecular solid electrolyte. However, the contact of the electron conductive polymer and the high molecular electrolyte at the interface is insufficient and then an interfacial resistance is increased, whereby a good electric conductivity is not obtained, and also the electrically conductive material is poor in mechanical strength.
Also, as a compound satisfying both the mechanical strength and the electric conducivity, the compound having a repeating unit of a carbazole group at the side chain having the structure shown below was investigated in No. 37 (1988) Kobunshi Toronkai (Polymer Forum) 2H04, but the electric conductivity was insufficient as from 1.times.10.sup.-4 to 1.times.10.sup.-5 S/cm. ##STR1##
Also, when polyaniline or a polyheterocyclic compound is used as a material for electrode, an anion is doped or dedoped with an oxidation reduction reaction. It is reported by Tekehara et al in No. 56 Denkikagaku Kai (Electrochemical Society) 3G24 that in the above-described case, the diffusion of the anion becomes the rate determination step.
As a practical method for preventing the diffusion of anion, a method of using an anionic compound as a doping agent is disclosed in JP-A-63-215772. However, in the method, there is a problem that with repeating doping, a concentration gradient occurs by the diffusion of the anionic compound, whereby the method does not provide a sufficiently improving means.